CN116515059A - ABABA type acrylate thermoplastic elastomer, controllable preparation method and application thereof - Google Patents

ABABA type acrylate thermoplastic elastomer, controllable preparation method and application thereof Download PDF

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CN116515059A
CN116515059A CN202310426675.1A CN202310426675A CN116515059A CN 116515059 A CN116515059 A CN 116515059A CN 202310426675 A CN202310426675 A CN 202310426675A CN 116515059 A CN116515059 A CN 116515059A
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monomer
initiator
acrylate
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tert
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王庆刚
朱广乾
王亮
杨树行
褚龙姣
匡佳
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof

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Abstract

ABABA type acrylate thermoplastic elastomer and controllable preparation method and application thereof. The present invention is in the field of acrylate polymers. The invention aims to solve the problem of lack of research on the multi-block acrylate elastomer, and solves the problems that the reaction time is long, the molecular weight distribution of the obtained polymer is wide, and the complete conversion of the monomer cannot be realized in the existing synthesis method of the tri-block acrylate elastomer. According to the invention, the methyl acrylic acid alkyl ester is used as the A section, the acrylic acid alkyl ester is used as the B section, an anionic polymerization method is utilized, and amine auxiliary agents are added at the same time to regulate and control the controllable progress of the polymerization reaction, so that the ABABABA type acrylic ester polymer is finally obtained, and the obtained polymer is high-temperature resistant, oil resistant, good in environment, and excellent in mechanical property, and can be applied to various fields of aerospace, national defense and military industry, automobile parts, lighting supplies, plastic modification and the like.

Description

ABABA type acrylate thermoplastic elastomer, controllable preparation method and application thereof
Technical Field
The invention belongs to the field of acrylate polymers, and particularly relates to an ABABA type acrylate thermoplastic elastomer, a controllable preparation method and application thereof.
Background
Thermoplastic elastomer (TPE) has elasticity of rubber at normal temperature, can be plasticized and molded at high temperature, and has dual performances and characteristics of rubber and plastic. The most widely used in the traditional TPE field are styrenic thermoplastic elastomers such as styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS) and its hydrides SEPS, SEBS, etc., which have important applications in plastic modifiers, hot melt pressure sensitive adhesives, etc. However, such elastomers suffer from certain drawbacks: the Tg of the styrene phase is lower, so that the use temperature range of the material is limited; meanwhile, the existence of benzene rings and unsaturated double bonds in the elastomer also affects the antioxidation and transparency of the elastomer.
The full-acrylate thermoplastic elastomer is a methacrylate-acrylate-methacrylate triblock copolymer obtained by catalytic polymerization reaction of methacrylate (hard segment) and acrylate (soft segment) monomers, is one of thermoplastic elastomer materials which are strategically developed, and has excellent mechanical property, transparency and oxidation resistance for the material by saturated carbon hydrogen bonds on a molecular main chain, and excellent oil resistance and sealing property for the material by polar ester functional groups on a molecular side chain. Meanwhile, the acrylic ester thermoplastic elastomer has a wider glass transition temperature range (-50-200 ℃) due to the rich monomer types (different side chain ester functional groups) of acrylic ester, and can meet the preparation requirement of thermoplastic elastomers with different use temperature ranges through the block copolymerization of different monomers. Therefore, the full-acrylate thermoplastic elastomer can be applied to various fields such as aerospace, national defense and military industry, automobile parts, illumination products, plastic modification and the like.
At present, researches on acrylate polymers mainly remain on diblock and triblock polymer systems, and a synthesis method of the triblock acrylate elastomer at present generally adopts free radical polymerization, so that the polymer obtained by the polymerization of the method has wide molecular weight distribution, can not realize complete conversion of monomers, and has long reaction time, thus being unfavorable for industrial production. Therefore, how to find a simple, efficient and novel polymerization method for realizing the controllable preparation of the multi-block acrylate polymer is an effective way for developing and widening the application of the acrylate elastomer in the new material field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ABABA type acrylate thermoplastic elastomer, a controllable preparation method and application thereof.
One of the purposes of the invention is to provide a controllable preparation method of an ABABBA type acrylic thermoplastic elastomer, which comprises the following steps:
under the anhydrous and anaerobic condition, adding a solvent, an amine auxiliary agent, a cocatalyst, an initiator and a comonomer into a reactor, wherein the comonomer is divided into a section A and a section B, the section A, the section B, the section A and the section A are sequentially added when the solvent, the amine auxiliary agent, the cocatalyst, the initiator and the comonomer are added, the reaction is carried out for a certain time at a certain temperature, then the next monomer is added, and after the polymerization reaction is finished, quenching, concentrating, washing and vacuum drying are carried out, so that the ABABBA type acrylic ester thermoplastic elastomer is obtained, wherein the section A monomer is alkyl methacrylate, and the section B monomer is alkyl acrylate.
Further defined, alkyl methacrylates include, but are not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, stearic methacrylate, the specific structure of which is shown below:
further defined, alkyl acrylates include, but are not limited to, one or more of n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, n-octyl acrylate, isooctyl acrylate, and the specific structures are as follows:
further defined, the amine auxiliary agent comprises one or more of diethylenetriamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, hexamethylphosphoric triamide, bis (hexamethylenetriamine), ethanolamine, triethylamine, triethanolamine, tripropylamine, ethylenediamine, N, N, N ', N ' -tetramethyl ethylenediamine, N, N ' -dimethylformamide, and the specific structure is as follows:
preferably, the amine auxiliary agent is one of pentamethyl diethylenetriamine, pentamethyl dipropylenetriamine, hexamethylphosphoric triamide and N, N, N ', N' -tetramethyl ethylenediamine.
More preferably, the amine adjuvant is pentamethyldiethylenetriamine or hexamethylphosphoric triamide.
Further defined, the initiator includes, but is not limited to, one or more of n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, n-propyllithium, isopropyllithium, phenyllithium, benzyllithium, and naphthalenelithium.
Preferably, the initiator is one of n-butyllithium, sec-butyllithium and tert-butyllithium.
More preferably, the initiator is sec-butyllithium.
Further defined, the solvent is one or more of amine auxiliary agent, benzene, toluene, ethylbenzene, xylene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethoxymethane.
Preferably, the solvent is toluene or ethylene glycol dimethyl ether.
Further defined, the cocatalyst is composed of AlR 3 Mixing with phenolic reagent according to the proportion of 1: the molar ratio of (1-5).
Preferably, the cocatalyst is selected from AlR 3 Mixing with phenolic reagent according to the proportion of 1:2 in molar ratio.
Further defined, alR 3 Is one of triethylaluminum, trimethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride and methylaluminoxane.
Preferably, alR 3 Is triisobutylaluminum or triethylaluminum.
More preferably, alR 3 Is triisobutylaluminum.
Further defined, the phenolic agent is one of the aryl phenols of different substituents.
Preferably, the phenolic reagent includes, but is not limited to, one of 2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl-p-methylphenol, 2, 6-di-tert-butyl-p-ethylphenol, 2,4, 6-tri-tert-butylphenol, 2, 6-diisopropylphenol, 2-tert-butylphenol, 2-tert-butyl-5-methylphenol, 2, 6-di-tert-butyl-4-nitrophenol.
More preferably, the phenolic reagent is 2, 6-di-t-butylphenol, 2, 6-di-t-butyl-p-cresol, 2, 6-di-t-butyl-p-ethylphenol or 2,4, 6-tri-t-butylphenol.
More preferably, the phenolic reagent is 2, 6-di-tert-butyl-p-methylphenol.
Further limited, the certain temperature is between-50 and 70 ℃, and the total polymerization time is between 3 and 24 hours.
Preferably, the certain temperature is-30-25 ℃, and the total polymerization time is 10 hours.
Further defined, the molar ratio of alkyl methacrylate monomer to alkyl acrylate monomer is 1: (1-10), the molar ratio of the amine auxiliary agent to the initiator is 1: (1-150), the ratio of the molar amount of the initiator to the total molar amount of the comonomer is 1: (100-5000), the ratio of the total mass of the comonomer to the mass of the solvent is 1: (0.2-5).
Preferably, the molar ratio of alkyl methacrylate monomer to alkyl acrylate monomer is 1: (1.5-4), the molar ratio of the amine auxiliary agent to the initiator is 1: (25-100), the ratio of the molar amount of the initiator to the total molar amount of the comonomer is 1: (400-800), the ratio of the total mass of the comonomer to the mass of the solvent being 1:3.
further limiting the vacuum drying temperature to be 30-100 ℃ and the time to be 12-36 h;
preferably, the temperature of the vacuum drying is 40 ℃ and the time is 24 hours.
The second object of the present invention is to provide an ABABA-type acrylate thermoplastic elastomer obtained according to the above method.
Further defined, the ABABA-type acrylate thermoplastic elastomer has a number average molecular weight (M n ) 1 to 50g/mol, a molecular weight distribution (PDI) of 1.1 to 2.0, and a block A with a syndiotacticity rr of 70 to 80%.
Preferably, the ABABA-type acrylate thermoplastic elastomer has a number average molecular weight (M n ) 6 to 12 g/mol, a molecular weight distribution (PDI) of 1.1 to 1.7, and a block A having a syndiotacticity rr of 73 to 78%.
The invention further aims to provide application of the ABABBA type acrylic ester thermoplastic elastomer obtained by the method in the fields of aerospace, national defense and military industry, automobile parts, lighting supplies and plastic modification.
Compared with the prior art, the invention has the remarkable effects that:
(1) Compared with the traditional method, the preparation method provided by the invention adopts a milder polymerization system, has simpler and more feasible reaction conditions, and is favorable for realizing industrial production.
(2) Compared with the additive used in the traditional method, the amine auxiliary agent used in the invention has the advantages of low toxicity, low price and the like, has better environmental-friendly advantage, and can effectively reduce the industrialization cost.
(3) The ABABA type acrylate thermoplastic elastomer prepared by the invention has the number average molecular weight of 1 ten thousand-50 ten thousand g/mol, the molecular weight distribution of 1.1-2.0, the syndiotactic regularity rr of PMMA block of 70-80%, better mechanical property, and excellent heat resistance, oxidation resistance and light transmittance, and can be applied to various fields such as aerospace, national defense and military industry, automobile parts, lighting supplies, plastic modification and the like.
Drawings
FIG. 1 is an ABABA type acrylate block polymer of example 1 1 HNMR spectra (400 MHz, CDCl) 3 ,298K)；
FIG. 2 is an ABABA type acrylate block polymer of example 1 13 C NMR spectrum (100 MHz, CDCl) 3 ,298K)；
FIG. 3 is a GPC chart of an ABABA type acrylate block polymer of example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
PMMA regularity analysis in the ABABBA type acrylate thermoplastic elastomer described in the examples below (in 13 In the C-NMR spectrum, the peak shapes at 44.5ppm, 44.8ppm and 45.5ppm all belong to the quaternary carbon of the methyl methacrylate block, and the three peaks represent rr, mr, mm stereoregularity respectively):
rr PMMA (％)＝[I 44.5 /(I 44.5 +I 44.8+ I 45.5 )]×100％。
example 1
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
60mL of toluene solvent, 60mL of amine auxiliary pentamethyldiethylenetriamine (2 mL,10mmol,25 equiv.) and promoter i-BuAl (BHT) were sequentially added to a 500mL schlenk flask under argon atmosphere 2 (8.89 mL,3.2mmol,8 equiv.), initiator s-BuLi (0.3 mL,0.4mmol,1 equiv.) and methyl methacrylate monomer (1.35 mL,12.5mmol,32.5 equiv.) are stirred at 25℃for one hour, the reaction flask is transferred to the low temperature reactor and n-butyl acrylate monomer (8.6 mL,60mmol, 150equiv.) is added thereto, the reaction flask in the low temperature reactor is taken out after stirring at-30℃for one hour and returned to room temperature, methyl methacrylate monomer (1.35 mL,12.5mmol,32.5 equiv.) is added thereto, stirring at 25℃is continued for three hours, the reaction flask is transferred again to the low temperature reactor and n-butyl acrylate (8.6 mL,60mmol, 150equiv.) is added thereto, stirring at-30℃is carried out for one hour, and the reaction flask in the low temperature reactor is returned to room temperature, and methyl acrylate monomer (1.35 mL,12.5 equiv.) is added thereto at 25℃for one hour. And (3) quenching with methanol and washing for three times, separating out a polymer, and drying to constant weight to obtain the ABABA type acrylate block polymer.
The yield is more than 99 percent. Wherein by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=25:75, conforming to the designed block ratio, wherein the a-block microstructure interstitials rr accounts for 73%; characterized by GPC: the number average molecular weight of the product was 67505g/mol and the molecular weight distribution was 1.33.
TABLE 1 molecular weight information Table
Peak M p (g/mol) M n (g/mol) M w (g/mol) M z (g/mol) M z+1 (g/mol) M v (g/mol) PDI
Peak1 58447 42276 54386 66402 77495 64717 1.286
Example 2
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
60mL of toluene solvent, 60mmol of amine adjuvant hexamethylphosphoric triamide (1.88 mL,10mmol,55 equiv.) and promoter i-BuAl (BHT) were sequentially added to a 500mL schlenk flask under argon atmosphere 2 (3.9 mL,1.40mmol,8 equiv.), initiator s-BuLi (0.14 mL,0.18mmol,1 equiv.) and methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) are stirred at 25℃for one hour, the reaction flask is transferred to a low temperature reactor and n-butyl acrylate monomer (8.06 mL,56.25mmol,312 equiv.) is added thereto, the reaction flask in the low temperature reactor is taken out after stirring at-30℃for one hour and returned to room temperature, methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) is added thereto for three hours, the reaction flask is transferred again to the low temperature reactor and n-butyl acrylate (8.06 mL,56.25mmol,312 equiv.) is added thereto, the reaction flask in-30℃is taken out after stirring for one hour, and the reaction flask is returned to room temperature after stirring at-30℃and methyl acrylate monomer (1.01 mL,9.38mmol,52 equiv.) is added thereto for three hours. And (3) quenching with methanol and washing for three times, separating out a polymer, and drying to constant weight to obtain the ABABA type acrylate block polymer.
The yield is more than 99 percent. Wherein by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=2:8, conforming to the designed block ratio, wherein the a-block microstructure interstitials rr ratio is 75%; characterized by GPC: the number average molecular weight of the product was 116474g/mol and the molecular weight distribution was 1.43.
Example 3
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
60mL of toluene solvent, 60mL of amine auxiliary agent N, N, N ', N' -tetramethyl ethylenediamine (2.2 mL,10mmol,55 equiv.) and promoter i-BuAl (BHT) were sequentially added to a 500mL schlenk flask under argon atmosphere 2 (3.9 mL,1.40mmol,8 equiv.), initiator s-BuLi (0.14 mL,0.18mmol,1 equiv.) and methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) at 25deg.CAfter stirring and reacting for one hour, transferring the reaction bottle into a low-temperature reactor, adding n-butyl acrylate monomer (8.06 mL,56.25mmol,312 equiv.) into the low-temperature reactor, stirring and reacting at-30 ℃ for one hour, taking out the reaction bottle in the low-temperature reactor, recovering to room temperature, adding methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) into the low-temperature reactor, continuing stirring and reacting for three hours at 25 ℃, transferring the reaction bottle into the low-temperature reactor again, adding n-butyl acrylate (8.06 mL,56.25mmol,312 equiv.) into the low-temperature reactor, stirring and reacting at-30 ℃ for a certain time, recovering to room temperature, adding methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) into the low-temperature reactor, and stirring and reacting at 25 ℃ for four hours. And (3) quenching with methanol and washing for three times, separating out a polymer, and drying to constant weight to obtain the ABABA type acrylate block polymer.
The yield is more than 99 percent. Wherein by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=2:8, conforming to the designed block ratio, wherein the a-block microstructure interstitials rr ratio is 75%; characterized by GPC: the number average molecular weight of the product was 114150g/mol and the molecular weight distribution was 1.55.
Example 4
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
60mL of toluene solvent, 60mL of pentamethyldiethylenetriamine (2 mL,10mmol,55 equiv.) as an amine auxiliary agent, and i-BuAl (BHT) as a cocatalyst were sequentially added to a 500mL schlenk flask under an argon atmosphere 2 (3.9 mL,1.404mmol,8 equiv.), initiator s-BuLi (0.14 mL,0.18mmol,1 equiv.) and hard monomer methyl methacrylate (1.01 mL,9.375mmol,52 equiv.) are stirred at 25℃for a certain period of time, the reaction vessel is transferred to a low temperature reactor to be charged with n-butyl acrylate monomer (8.06 mL,56.25mmol,312 equiv.) and the reaction vessel is taken out of the low temperature reactor to be returned to room temperature after stirring at-30℃for one hour, the stirring reaction is continued with the methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) being added, the reaction vessel is transferred again to the low temperature reactor to be charged with n-butyl acrylate (8.06 mL,56.25mmol,312 equiv.) after stirring at 25℃for three hours, the reaction vessel is taken out of the low temperature reactor after stirring at-30℃for one hour, and the methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) is added to be continuously stirred at room temperatureEster monomer (1.01 mL,9.38mmol,52 equiv.) was reacted for four hours at 25 ℃. And (3) quenching with methanol and washing for three times, separating out a polymer, and drying to constant weight to obtain the ABABA type acrylate block polymer.
The yield is more than 99 percent. Characterization by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=2:8, conforming to the designed block ratio, wherein the a-block microstructure interstitials rr accounts for 74%; characterized by GPC: the number average molecular weight of the product was 115624g/mol and the molecular weight distribution was 1.34.
Example 5
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
60mL of toluene solvent, 60mL of pentamethyldiethylenetriamine (4.5 mL,18mmol,100 equiv.) as an amine auxiliary agent, and i-BuAl (BHT) as a cocatalyst were sequentially added to a 500mL schlenk flask under an argon atmosphere 2 (3.9 mL,1.4mmol,8 equiv.), initiator s-BuLi (0.14 mL,0.18mmol,1 equiv.) and hard monomer methyl methacrylate (1.01 mL,9.38mmol,52 equiv.) are stirred at 25℃for one hour, the reaction flask is transferred to the low temperature reactor and n-butyl acrylate monomer (8.06 mL,56.25mmol,312 equiv.) is added thereto, the reaction flask in the low temperature reactor is taken out after stirring at-30℃for one hour and returned to room temperature, methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) is added thereto, stirring at 25℃is continued for three hours, the reaction flask is transferred again to the low temperature reactor and n-butyl acrylate (8.06 mL,56.25mmol,312 equiv.) is added thereto, stirring at-30℃for one hour, and the reaction flask in the low temperature is taken out and returned to room temperature, and methyl methacrylate monomer (1.01 mL,9.38 mmol) is added thereto at 25℃for one hour. And (3) quenching with methanol and washing for three times, separating out a polymer, and drying to constant weight to obtain the ABABA type acrylate block polymer.
The yield is more than 99 percent. Characterization by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=2:8, conforming to the designed block ratio, wherein the a-block microstructure interstitials rr accounts for 74%; characterized by GPC: the number average molecular weight of the product was 118925g/mol and the molecular weight distribution was 1.26.
Example 6
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
60mL of toluene solvent, 60mL of pentamethyldiethylenetriamine (2 mL,10mmol,55 equiv.) as an amine auxiliary agent, and i-BuAl (BHT) as a cocatalyst were sequentially added to a 500mL schlenk flask under an argon atmosphere 2 (3.9 mL,1.40mmol,8 equiv.), initiator s-BuLi (0.14 mL,0.18mmol,1 equiv.) and hard monomer methyl methacrylate (1.01 mL,9.38mmol,52 equiv.) are stirred at 25℃for one hour, the reaction flask is transferred to the low temperature reactor and n-butyl acrylate monomer (8.06 mL,56.25mmol,312 equiv.) is added thereto, the reaction flask in the low temperature reactor is taken out after stirring at-30℃for one hour and returned to room temperature, methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) is added thereto, stirring at 25℃is continued for three hours, the reaction flask is transferred again to the low temperature reactor and n-butyl acrylate (8.06 mL,56.25mmol,312 equiv.) is added thereto, stirring at-30℃for one hour, the reaction flask in the low temperature is taken out and returned to room temperature, and methyl methacrylate monomer (1.01 mL,9.38 mmol) is added thereto, stirring at 25℃is continued. And (3) quenching with methanol and washing for three times, separating out a polymer, and drying to constant weight to obtain the ABABA type acrylate block polymer.
The yield is more than 99 percent. Characterization by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=2:8, conforming to the designed block ratio, wherein the a-block microstructure interstitials rr ratio is 75%; characterized by GPC: the number average molecular weight of the product was 107505g/mol and the molecular weight distribution was 1.33.
Example 7
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
60mL of ethylene glycol dimethyl ether solvent, amine auxiliary agent pentamethylene diethylenetriamine (2 mL,10mmol,55 equiv.) and promoter i-BuAl (BHT) are sequentially added into a 500mL schlenk flask under argon atmosphere 2 (3.9 mL,1.4mmol,8 equiv.), initiator s-BuLi (0.14 mL,0.18mmol,1 equiv.) and hard monomer methyl methacrylate (1.01 mL,9.38mmol,52 equiv.) were reacted for one hour with stirring at 25℃the reaction flask was transferred to a low temperature reactor and n-butyl acrylate monomer (8.06 mL,56.25mmol,312 equiv.) was added.) Stirring at-30 ℃ for one hour, taking out the reaction bottle in the low-temperature reactor, recovering to room temperature, adding methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) for continuous stirring reaction, stirring at 25 ℃ for three hours, transferring the reaction bottle into the low-temperature reactor again, adding n-butyl acrylate (8.06 mL,56.25mmol,312 equiv.) for one hour, stirring at-30 ℃ for one hour, taking out the reaction bottle in the low-temperature reaction bottle, recovering to room temperature, adding methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) for stirring at 25 ℃ for four hours. And (3) quenching with methanol and washing for three times, separating out a polymer, and drying to constant weight to obtain the ABABA type acrylate block polymer.
The yield is more than 99 percent. Characterization by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=2:8, conforming to the designed block ratio, wherein the a-block microstructure interstitiality rr ratio is 78%; characterized by GPC: the number average molecular weight of the product was 116219g/mol and the molecular weight distribution was 1.57.
Example 8
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
under argon atmosphere, 60mL of anisole solvent, 60mmol of amine auxiliary agent pentamethyldiethylenetriamine (2 mL,10mmol,55 equiv.) and promoter i-BuAl (BHT) are sequentially added into a 500mL schlenk flask 2 (3.9 mL,1.4mmol,8 equiv.), initiator s-BuLi (0.14 mL,0.18mmol,1 equiv.) and hard monomer methyl methacrylate (1.01 mL,9.38mmol,52 equiv.) are stirred at 25℃for one hour, the reaction flask is transferred to the low temperature reactor and n-butyl acrylate monomer (8.06 mL,56.25mmol,312 equiv.) is added thereto, the reaction flask in the low temperature reactor is taken out after stirring at-30℃for one hour and returned to room temperature, methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) is added thereto, stirring at 25℃is continued for three hours, the reaction flask is transferred again to the low temperature reactor and n-butyl acrylate (8.06 mL,56.25mmol,312 equiv.) is added thereto, stirring at-30℃for one hour, and the reaction flask in the low temperature is taken out and returned to room temperature, and methyl methacrylate monomer (1.01 mL,9.38 mmol) is added thereto at 25℃for one hour. Quenching with methanol and washing three times, precipitating polymer, and drying to constant weightTo obtain the ABABBA type acrylic ester block polymer.
The yield is more than 99 percent. Characterization by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=2:8, conforming to the designed block ratio, wherein the a-block microstructure interstitiality rr ratio is 77%; characterized by GPC: the number average molecular weight of the product was 114132g/mol and the molecular weight distribution was 1.70.
Example 9
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
under argon, 37.5mL of toluene solvent, the amine adjuvant pentamethyldiethylenetriamine (2 mL,10mmol,55 equiv.) and the cocatalyst i-BuAl (BHT) were sequentially added to a 500mL schlenk flask 2 (3.9 mL,1.404mmol,8 equiv.), initiator s-BuLi (0.14 mL,0.18mmol,1 equiv.) and hard monomer methyl methacrylate (1.01 mL,9.38mmol,52 equiv.) are stirred at 25℃for one hour, the reaction flask is transferred to the low temperature reactor and n-butyl acrylate monomer (4.7 mL,32.8mmol,182 equiv.) is added thereto, the reaction flask in the low temperature reactor is taken out after stirring at-30℃for one hour and returned to room temperature, methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) is added thereto, stirring at 25℃is continued for three hours, the reaction flask is transferred again to the low temperature reactor and n-butyl acrylate (4.7 mL,32.8mmol,182 equiv.) is added thereto, stirring at-30℃for one hour, the reaction flask in the low temperature is taken out and the reaction flask is returned to room temperature, and methyl methacrylate monomer (1.01 mL, 52 equiv.) is added thereto at 25℃for one hour. And (3) quenching with methanol and washing for three times, separating out a polymer, and drying to constant weight to obtain the ABABA type acrylate block polymer.
The yield is more than 99 percent. Characterization by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=3:7, conforming to the designed block ratio, wherein the a-block microstructure interstitiality rr accounts for 76%; characterized by GPC: the number average molecular weight of the product was 78429g/mol and the molecular weight distribution was 1.28.
Example 10
The preparation steps of the ABABA type acrylate thermoplastic elastomer of this example are as follows:
under argon atmosphere, 500mL30mL of toluene solvent, pentamethyldiethylenetriamine (2 mL,10mmol,55 equiv.) as an amine ligand additive, and i-BuAl (BHT) as a cocatalyst were sequentially added to a schlenk flask 2 (3.9 mL,1.4mmol,8 equiv.), initiator s-BuLi (0.14 mL,0.18mmol,1 equiv.) and hard monomer methyl methacrylate (1.01 mL,9.38mmol,52 equiv.) are stirred at 25℃for one hour, the reaction flask is transferred to the low temperature reactor, n-butyl acrylate monomer (3 mL,21.09mmol,117 equiv.) is added, the reaction flask in the low temperature reactor is taken out after stirring at-30℃for one hour and returned to room temperature, methyl methacrylate monomer (1.01 mL,9.38mmol,52 equiv.) is added, stirring at 25℃is continued for three hours, the reaction flask is transferred again to the low temperature reactor, n-butyl acrylate (3 mL,21.09mmol,117 equiv.) is added, stirring at-30℃is carried out for one hour, the reaction flask in the low temperature reaction is returned to room temperature, and methyl acrylate monomer (1.01 mL,9.38mmol,52 equiv.) is added at 25℃for four hours. And (3) quenching with methanol and washing for three times, separating out a polymer, and drying to constant weight to obtain the ABABA type acrylate block polymer.
The yield is more than 99 percent. Characterization by NMR: the ratio of methyl methacrylate to n-butyl acrylate block=4:6, conforming to the designed block ratio, wherein the a-block microstructure interstitials rr ratio is 75%; characterized by GPC: the number average molecular weight of the product was 59413g/mol and the molecular weight distribution was 1.25.
In the foregoing, the present invention is merely preferred embodiments, which are based on different implementations of the overall concept of the invention, and the protection scope of the invention is not limited thereto, and any changes or substitutions easily come within the technical scope of the present invention as those skilled in the art should not fall within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (15)

1. A controllable preparation method of an ABABA type acrylate thermoplastic elastomer, which is characterized by comprising the following steps:
under the anhydrous and anaerobic condition, adding a solvent, an amine auxiliary agent, a cocatalyst, an initiator and a comonomer into a reactor, wherein the comonomer is divided into a section A and a section B, the section A, the section B, the section A and the section A are sequentially added when the solvent, the amine auxiliary agent, the cocatalyst, the initiator and the comonomer are added, the reaction is carried out for a certain time at a certain temperature, then the next monomer is added, and after the polymerization reaction is finished, quenching, concentrating, washing and vacuum drying are carried out, so that the ABABBA type acrylic ester thermoplastic elastomer is obtained, wherein the section A monomer is alkyl methacrylate, and the section B monomer is alkyl acrylate.
2. The method of claim 1, wherein the alkyl methacrylate includes, but is not limited to, one or more of the following structures:
alkyl acrylates include, but are not limited to, one or more of the following structures:
3. the method of claim 1, wherein the amine-based adjuvant includes, but is not limited to, one or more of the following structures:
the initiator comprises one or more of n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, n-propyllithium, isopropyllithium, phenyllithium, benzyllithium and naphthyllithium, the solvent is one or more of amine auxiliary agent, benzene, toluene, ethylbenzene, xylene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethoxymethane, and the promoter is AlR 3 Mixing with phenolic reagent according to the proportion of 1: the molar ratio of (1-5).
4. The method according to claim 3, wherein the amine auxiliary agent is one of pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, hexamethylphosphoric triamide and N, N, N ', N' -tetramethyl ethylenediamine, the initiator is one of N-butyllithium, sec-butyllithium and tert-butyllithium, the solvent is toluene or ethylene glycol dimethyl ether, and the promoter is AlR 3 Mixing with phenolic reagent according to the proportion of 1:2 in molar ratio.
5. The process according to claim 4, wherein the amine auxiliary is pentamethyldiethylenetriamine or hexamethylphosphoric triamide and the initiator is sec-butyllithium.
6. A method according to claim 3, wherein AlR 3 Is one of triethylaluminum, trimethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride and methylaluminoxane, and the phenolic reagent is one of aryl phenols with different substituents.
7. The method of claim 6, wherein AlR 3 The phenolic reagent is triisobutylaluminum or triethylaluminum, and includes but is not limited to one of 2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl-p-methylphenol, 2, 6-di-tert-butyl-p-ethylphenol, 2,4, 6-tri-tert-butylphenol, 2, 6-diisopropylphenol, 2-tert-butylphenol, 2-tert-butyl-5-methylphenol, 2, 6-di-tert-butyl-4-nitrophenol.
8. The method of claim 7, wherein the phenolic agent is 2, 6-di-t-butylphenol, 2, 6-di-t-butyl-p-cresol, 2, 6-di-t-butyl-p-ethylphenol, or 2,4, 6-tri-t-butylphenol.
9. The method according to claim 1, wherein the polymerization time is 3 to 24 hours at a temperature of-50 to 70 ℃.
10. The process according to claim 9, wherein the polymerization is carried out for a total time of 10 hours at a temperature of-30 to 25 ℃.
11. The method of claim 1, wherein the molar ratio of alkyl methacrylate monomer to alkyl acrylate monomer is 1: (1-10), the molar ratio of the amine auxiliary agent to the initiator is 1: (1-150), the ratio of the molar amount of the initiator to the total molar amount of the comonomer is 1: (100-5000), the ratio of the total mass of the comonomer to the mass of the solvent is 1: (0.2-5).
12. The method of claim 11, wherein the molar ratio of alkyl methacrylate monomer to alkyl acrylate monomer is 1: (1.5-4), the molar ratio of the amine auxiliary agent to the initiator is 1: (25-100), the ratio of the molar amount of the initiator to the total molar amount of the comonomer is 1: (400-800), the ratio of the total mass of the comonomer to the mass of the solvent being 1:3.
13. an ABABA-type acrylate thermoplastic elastomer obtained by the process according to any of the claims 1-12, characterized in that the elastomer is M n 1 to 50g/mol, PDI is 1.1 to 2.0, and the syndiotactic regularity rr of the A block is 70 to 80 percent.
14. ABABA-type acrylate thermoplastic elastomer according to claim 13, characterized in that it is M n The PDI is 1.1-1.7, and the syndiotactic regularity rr of the A block is 73-78% at 6-12 g/mol.
15. Use of ABABA-type acrylate thermoplastic elastomers obtained by the method of any of claims 1-12 in the fields of aerospace, defense and military, automotive parts, lighting applications and plastic modification.
CN202310426675.1A 2023-04-20 2023-04-20 ABABA type acrylate thermoplastic elastomer, controllable preparation method and application thereof Pending CN116515059A (en)

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